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US3810974A - Aluminum hydride preparation - Google Patents

Aluminum hydride preparation Download PDF

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Publication number
US3810974A
US3810974A US00366933A US36693364A US3810974A US 3810974 A US3810974 A US 3810974A US 00366933 A US00366933 A US 00366933A US 36693364 A US36693364 A US 36693364A US 3810974 A US3810974 A US 3810974A
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Prior art keywords
aluminum hydride
ether
distillation
solution
stable
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US00366933A
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W King
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Aerojet Rocketdyne Inc
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Aerojet General Corp
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Priority to US00366933A priority Critical patent/US3810974A/en
Priority to AU60785/73A priority patent/AU6078573A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00Explosive and thermic compositions or charges
    • Y10S149/12High energy fuel compounds

Definitions

  • Aluminum hydride is known to be useful as a fuel in solid propellants for rocket propulsion. Until recently aluminum hydride existed only in the form of an etherate and if any attempt was made to remove the ether by heating, the aluminum hydride decomposed.
  • lithium aluminum hydride As indicated in the above reaction scheme, a one mole excess of lithium aluminum hydride is employed.
  • the lithium chloride may be removed by any liquid-solid separation means such as decantation, centrifugation or filtration and the ether solution heated under vacuum .to produce stable aluminum hydride powder.
  • Aluminum hydride in the form of a powder has very undesirable characteristics in the formation of a solid propellant.
  • the powder tends to cake into lumps and even distribution of the aluminum hydride throughout the propellant is impossible. s
  • the present invention resides in a method for recovering the aluminum hydride produced as disclosed in the reaction scheme discussed above, in which an improved crystalline form of aluminum hydride is recovered rather than the powdered form of the prior art as shown above.
  • the precipitate of LiCl was allowed to settle and the supernatent solution was pumped by argon pressure througha glass wool filter into a one liter pressure equilibrated dropping funnel. This solution was then added to 3,400 ml. of toluene un-' der an argon-atmosphere. The ether-toluene solution was completely'free' of precipitate. The solution was added to a 5 liter round bottom flask fitted'with a stirrer, thermometer, a distillation head, and an electrically heated oil bath. The solvent was distilled according to the following schedule: 1
  • benzene and xylene may also be used although the crystals of aluminum hydride obtained using benzene and xylene are less desirable.
  • the procedure discussed above may be modified to obtain mono-crystalline chunks of aluminum hydride by carrying out the initial distillation step at a temperature between about 65 C. and about C. rather than at about 50C. to about 65 C.
  • the distillation may be carried out between about 50 C. and about 65 C.
  • the intermediate etherate forms and is converted to the stable aluminum hydride.
  • the etherate form of aluminum hydride is bypassed and a stable form precipitates immediately. In this upper range even less decrepitation occurs and larger chunks of stable aluminum hydride are recovered.
  • EXAMPLE 2 An ether solution of aluminum hydride was prepared as disclosed in Example 1 above. The solution was added to 3,400 ml. of toluene and the ether-toluene solution was distilled from a liter fiask equipped with a thermometer, stirrer, take-01f head and oil bath according to the following schedule:
  • the flask was cooled and the contents transferred to a separatory funnel.
  • the ether-toluene solution was withdrawn after the solid had settled.
  • the solid was washed with 3 successive 500 ml. portions of ether and the ether was decanted until it remained clear during the washing.
  • the product was then collected on a sintered glass filter and dried with an argon stream for one hour and then under vacuum overnight.
  • the yield was a monocrystalline form of aluminum hydride in which the crystals were the size of about 30 to 50 microns in diameter.
  • a large excess of solvent i.e. toluene, is employed in the distillation procedure-at least three, preferably at least five times the volume of the ether solution.
  • the solvent is substantially dry, that is, contains less than about .1% water and preferably is even drier.
  • the pressure and temperature at which distillation of the ether is conducted may vary, the important. feature being raising the temperature for conversion while about 8 to 10 percent of ether remains in solution.
  • the pressure during distillation may vary from about 175 mm. Hg to about 500 mm. Hg, a lower pressure being required at lower temperatures, and during conversion preferably atmospheric pressure is employed.
  • the temperature during distillation may vary from about 50 C. to about 85 C., and during conversion from about 90 C. to about 100 0.
  • a process for producing aluminum hydride of an improved stable crystalline form comprising:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Abstract

THIS INVENTION RELATES TO A NOVEL FORM OF ALUMINUM HYDRIDE AND A METHOD FOR ITS PREPARATION.

Description

United States Pate-n1: once Mj'ilffiii 3,810,974 ALUMINUM HYDRIDE PREPARATION William M. King, Walnut, Calif., assignor to Aerojet- General Corporation, Azusa, Calif. No Drawing. Filed May 5, 1964, Ser. No. 366,933 Int. Cl. C01b 6/00 US. Cl. 423-645 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a novel form of aluminum hydride and a method for its preparation.
Aluminum hydride is known to be useful as a fuel in solid propellants for rocket propulsion. Until recently aluminum hydride existed only in the form of an etherate and if any attempt was made to remove the ether by heating, the aluminum hydride decomposed.
A process has recently been developed for producing a stable form of aluminum hydride in the form of a fine powder. It was found that if an excess, preferably a one mole excess, of lithium aluminum hydride was utilized in the initial reactions, the ether solution in which the reac-' tion takes place may be removed under vacuum to obtain a stable form of aluminum hydride as a fine powder. The reaction scheme is indicated as follows:
As indicated in the above reaction scheme, a one mole excess of lithium aluminum hydride is employed. The lithium chloride may be removed by any liquid-solid separation means such as decantation, centrifugation or filtration and the ether solution heated under vacuum .to produce stable aluminum hydride powder.
Aluminum hydride in the form of a powder has very undesirable characteristics in the formation of a solid propellant. The powder tends to cake into lumps and even distribution of the aluminum hydride throughout the propellant is impossible. s
It is an object of the present invention to provide stable aluminum hydride in a crystalline form.
It is a further object of this invention to provide a prooess for the production of aluminum hydride in a crystalline form which is less reactive chemically, is thermally more stable and possesses superior physical characteristics for the production of solid propellants.
It has been known to recover aluminum hydride powder out of an ether-toluene solution containing excess lithium aluminum hydride by distillation at reduced pressure. This is accomplished by first precipitating out aluminum hydride etherate by distillation at about 50 C. to about 65 C. until only 3 to 5 percent of the ether remains in the toluene. This system is then brought up to atmospheric pressure, and the temperature is raised to about 90 to about 100 C. The aluminum hydride etherate is then converted to aluminum hydride powder after approximately 40 minutes at about 90 to about 100 C.
The present invention resides in a method for recovering the aluminum hydride produced as disclosed in the reaction scheme discussed above, in which an improved crystalline form of aluminum hydride is recovered rather than the powdered form of the prior art as shown above.
It has been found that the retention of 8 to 10 percent of the ether after the initial distillation step results in a superior final product. The retention of this other permits rearrangement of aluminum hydride during the conversion to the stable form of aluminum hydride. The decrepitation of the crystal is reduced and the final product is crystalline rather than the powder previously obtained. The chemical reactivity, thermal stability and bulk density are iiiiiiivd "062.111.; passage. estates passe-ed EXAMPLE 1 400 m1. of a 1 M solution of LiAlH in ether was added under an argon atmosphere to 100 ml. of 1 M AlCl in ether in a 1 liter graduated cylinder. The cylinder was stoppered and shaken to mix the contents. The precipitate of LiCl was allowed to settle and the supernatent solution was pumped by argon pressure througha glass wool filter into a one liter pressure equilibrated dropping funnel. This solution was then added to 3,400 ml. of toluene un-' der an argon-atmosphere. The ether-toluene solution was completely'free' of precipitate. The solutionwas added to a 5 liter round bottom flask fitted'with a stirrer, thermometer, a distillation head, and an electrically heated oil bath. The solvent was distilled according to the following schedule: 1
Pot Oil temp., temp., Pressure, Time, min. 0. 0. mm. Hg Remarks 100 200 Distillation begins. 59 75 200 Precipitation begins. 69 75 760 8-10 ether remains. 93 105 760 98 110 760 99 110 760 The flask was cooled to room temperature and the contents were transferred to a large separatory funnel and the solid was allowed to settle. The supernatent liquid was pumped out with argon pressure and the product was washed with three 500 ml. portions of dry ether. A final 500 ml. portion of dry ether was added and the suspension was filtered through a sintered glass filter attached to the bottom of the separatory funnel with a rubber stopper, using argon pressure through the funnel. The argon stream was continued for 1 hour to dry the product which was further dried in a vacuum desiccator overnight. Mono-crystalline particles ofaluminum hydride of the size up to aboutv 30 microns in diameterwere recovc red.
While the preparation of aluminum hydride was carried out in the example above using aluminum chloride,
it is well known that hydrogen chloride may be substituted for the aluminum chloride.
Although toluene is preferred as solvent for the distillation step, benzene and xylene may also be used although the crystals of aluminum hydride obtained using benzene and xylene are less desirable.
The procedure discussed above may be modified to obtain mono-crystalline chunks of aluminum hydride by carrying out the initial distillation step at a temperature between about 65 C. and about C. rather than at about 50C. to about 65 C.
The distillation may be carried out between about 50 C. and about 65 C. At the lower end of this range, on the order of about 50 C. to about 65 C. the intermediate etherate forms and is converted to the stable aluminum hydride. However, at the upper end of this range on the order of about 65 C. to about 85 C., the etherate form of aluminum hydride is bypassed and a stable form precipitates immediately. In this upper range even less decrepitation occurs and larger chunks of stable aluminum hydride are recovered.
EXAMPLE 2 An ether solution of aluminum hydride was prepared as disclosed in Example 1 above. The solution was added to 3,400 ml. of toluene and the ether-toluene solution was distilled from a liter fiask equipped with a thermometer, stirrer, take-01f head and oil bath according to the following schedule:
Pressure,
mm. Hg Remarks Distillation begins. Precipitation begins. 8-l0% ether remains.
The flask was cooled and the contents transferred to a separatory funnel. The ether-toluene solution was withdrawn after the solid had settled. The solid was washed with 3 successive 500 ml. portions of ether and the ether was decanted until it remained clear during the washing. The product was then collected on a sintered glass filter and dried with an argon stream for one hour and then under vacuum overnight. The yield was a monocrystalline form of aluminum hydride in which the crystals were the size of about 30 to 50 microns in diameter.
A large excess of solvent, i.e. toluene, is employed in the distillation procedure-at least three, preferably at least five times the volume of the ether solution. For best results the solvent is substantially dry, that is, contains less than about .1% water and preferably is even drier.
The pressure and temperature at which distillation of the ether is conducted may vary, the important. feature being raising the temperature for conversion while about 8 to 10 percent of ether remains in solution.
The pressure during distillation may vary from about 175 mm. Hg to about 500 mm. Hg, a lower pressure being required at lower temperatures, and during conversion preferably atmospheric pressure is employed.
The temperature during distillation may vary from about 50 C. to about 85 C., and during conversion from about 90 C. to about 100 0.
Having fully described the product, its method of preparation and its utilities, it is desired that the invention be limited only within the lawful scope of the appended claims.
I claim:
1. A process for producing aluminum hydride of an improved stable crystalline form, said process comprising:
(1) reacting AlCl with LiAlH; with the AlCl being present in one mole per about four moles of the LiAlH in an ether solvent to form an ether solution of AlH and a precipitate of LiCl (2) separating the LiCl precipitate from the ether solution;
(3) mixing the ether solution with an aromatic solvent, said aromatic solvent being present in at least three volumes per volume of ether solution, and carrying on a distillation under a subatmospheric pressure of about 175 mm. Hg to about 500 mm. Hg and ate temperature in the range of about C. to about 85 C. until the ether is present in the distillant in an amount of about 8 to about 10 percent;
(4) discontinuing the subatmospheric distillation and raising the temperature of the distillant to convert the aluminum hydride to a stable form; and
(5) recovering a stable aluminum hydride product.
2. A process in accordance with claim 1 wherein the aromatic solvent employed is toluene.
3. A process in accordance with claim 1 wherein 'the;v subatmospheric distillation is carried on at a temperature in the range of about 50 C. to about C.
4. A process in accordance with claim 1 wherein the subatmospheric distillation is carried on at a temperature in the range of about 65 C. to about C.
5. A process in accordance with claim 1 wherein the conversion to the stable aluminum hydride form is carried on at a temperature of about C. to about C.
1958 Germany 23204 OTHER REFERENCES Non-solvated Aluminum Hydride, Rice, Aug. 1, 1956, Technical Report to the Ofiice of Naval Research, Contract ONR494(04) pp. 1-5.
LELAND A. SEBASTIAN, Primary Examiner US. Cl. X.R. 149-109
US00366933A 1964-05-05 1964-05-05 Aluminum hydride preparation Expired - Lifetime US3810974A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670129A (en) * 1994-12-24 1997-09-23 Th. Goldschmidt Ag. Method for synthesizing aluminum hydride
US6228338B1 (en) 1999-06-16 2001-05-08 Sri International Preparation of aluminum hydride polymorphs, particularly stabilized α-alh3
US20050222445A1 (en) * 2004-04-05 2005-10-06 Lund Gary K Method for the production of alpha-alane
US20070066839A1 (en) * 2004-04-05 2007-03-22 Lund Gary K Method for the production of alpha-alane
WO2013184617A1 (en) 2012-06-05 2013-12-12 Eveready Battery Company, Inc Method of manufacturing alane including desolvation of an alane -etherate complex
WO2013184616A1 (en) 2012-06-05 2013-12-12 Eveready Battery Company, Inc Method for preparation of alane-etherate and alane
WO2014058528A1 (en) 2012-10-09 2014-04-17 Intelligent Energy, Inc. Method for preparation of crystalline alane using quaternary ammonium aluminum hydride
US9228267B1 (en) 2011-11-07 2016-01-05 Ardica Technologies, Inc. Use of fluidized-bed electrode reactors for alane production
US9327974B1 (en) 2011-11-07 2016-05-03 Ardica Technologies, Inc. Aluminum hydride production
US9550672B2 (en) 2012-06-05 2017-01-24 Intelligent Energy Inc. Method for preparation of an alane-etherate complex and alane
US9676625B1 (en) 2011-11-07 2017-06-13 Ardica Technologies, Inc. Synthesis of microcrystalline alpha alane
US10233079B2 (en) 1999-06-16 2019-03-19 Ardica Technologies, Inc. Heating methods for aluminum hydride production
US10246785B2 (en) 2011-11-07 2019-04-02 Ardica Technologies, Inc. Use of fluidized-bed electrode reactors for alane production
US10435297B2 (en) 1999-06-16 2019-10-08 Ardica Technologies, Inc. Crystallization and stabilization in the synthesis of microcrystalline alpha alane

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670129A (en) * 1994-12-24 1997-09-23 Th. Goldschmidt Ag. Method for synthesizing aluminum hydride
US6228338B1 (en) 1999-06-16 2001-05-08 Sri International Preparation of aluminum hydride polymorphs, particularly stabilized α-alh3
US6617064B2 (en) 1999-06-16 2003-09-09 Sri International Stabilized aluminum hydride polymorphs
US10435297B2 (en) 1999-06-16 2019-10-08 Ardica Technologies, Inc. Crystallization and stabilization in the synthesis of microcrystalline alpha alane
US10233079B2 (en) 1999-06-16 2019-03-19 Ardica Technologies, Inc. Heating methods for aluminum hydride production
US20050222445A1 (en) * 2004-04-05 2005-10-06 Lund Gary K Method for the production of alpha-alane
WO2005102919A1 (en) * 2004-04-05 2005-11-03 Alliant Techsystems, Inc. METHOD FOR THE PRODUCTION OF α-ALANE
US6984746B2 (en) 2004-04-05 2006-01-10 Alliant Techsystems Inc. Method for the production of α-alane
US20070066839A1 (en) * 2004-04-05 2007-03-22 Lund Gary K Method for the production of alpha-alane
US7238336B2 (en) 2004-04-05 2007-07-03 Alliant Techsystems Inc. Method for the production of α-alane
US9327974B1 (en) 2011-11-07 2016-05-03 Ardica Technologies, Inc. Aluminum hydride production
US9228267B1 (en) 2011-11-07 2016-01-05 Ardica Technologies, Inc. Use of fluidized-bed electrode reactors for alane production
US9676625B1 (en) 2011-11-07 2017-06-13 Ardica Technologies, Inc. Synthesis of microcrystalline alpha alane
US10246785B2 (en) 2011-11-07 2019-04-02 Ardica Technologies, Inc. Use of fluidized-bed electrode reactors for alane production
US9550672B2 (en) 2012-06-05 2017-01-24 Intelligent Energy Inc. Method for preparation of an alane-etherate complex and alane
WO2013184616A1 (en) 2012-06-05 2013-12-12 Eveready Battery Company, Inc Method for preparation of alane-etherate and alane
WO2013184617A1 (en) 2012-06-05 2013-12-12 Eveready Battery Company, Inc Method of manufacturing alane including desolvation of an alane -etherate complex
WO2014058528A1 (en) 2012-10-09 2014-04-17 Intelligent Energy, Inc. Method for preparation of crystalline alane using quaternary ammonium aluminum hydride

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